Triazole/thiazole amino-s-triazine bonding agents

ABSTRACT

A compound contains a ligand group and at least one group of the general formula --XR n  where X is a linking group which contains at least one hetero-atom, R is a saturated hydrocarbyl group containing at least six carbon atoms or is an unsaturated hydrocarbyl group containing at least three carbon atoms. The ligand group can be a polyhydroxyhydrocarbyl, a triazole, an imidazole, an indazole, a thiazole, an oxazole, a carbamate, an xanthate or a phthalazine. The compounds can be used to improve bonding between a metal and a coating material in contact with the metal surface. The metal may be a tire cord and the coating material rubber or a rubber composition.

This is a divisional of co-pending application Ser. No. 07/301,785 filedon Jan. 25, 1989 now U.S. Pat. No. 4,978,756.

The present invention relates to new compounds and the use of suchcompounds for the treatment of metal, more specifically for use incontact with the surface of a metal to provide improved corrosionresistance, or improved bonding, or both.

It is known to apply chemicals or mixtures of chemicals to the surfaceof metals in order to improve the corrosion resistance of such metals.Processes for improving the corrosion resistance of metals have beenextensively described, inter alia in European Patent ApplicationsPublication Nos. 126030 and 134699 and British Patent Specification No.2104107.

It is also known to apply chemicals or mixtures of chemicals to thesurface of metals to improve the adhesion of a surface composition tothe surface of the metal. In particular, it is known to apply a coatingto a metal surface which improves the strength of an adhesive bond whenan adhesive composition is applied to the coated metal surface.Compounds which can be used to give improved adhesion are typicallycalled adhesion promoters. Such compounds can be used to improve bondingin production of composite articles or in the production of printedcircuit boards. An effective class of adhesion promoter for bonding ofcopper substrates is disclosed in U.S. Pat. No. 3,837,964. Otheradhesion promoters are disclosed in U.S. Pat. Nos. 4,428,987 and4,448,847. Organosilanes can be used as adhesion promoters, such as, forexample gamma-glycidoxypropyltrimethoxysilane and other silanescontaining a functional substituent.

Good adhesion between rubber and metal is of considerable importance inrubber articles which contain metal reinforcement. A wide range ofrubber articles have metal reinforcement, for example power transmissionbelts, conveyor belts and rubber hoses. Probably the best known use ofmetal reinforcement of rubber is in tires, many of which are nowreinforced with metal tire cords where the metal is either steel orbrass-coated steel. Many compounds have been proposed to improve theadhesion between rubber and metals which can be used as reinforcement.Substituted s-triazine compounds, and their use in bonding metal torubber, are described in GB 1419631, GB 1419632 and GB 1504375. The useof a range of imidazolidinone compounds to form a strong adhesive bondbetween a vulcanised rubber and a metal reinforcing member is describedin U.S. Pat. No. 4,284,536 and U.S. Pat. No. 4,300,973. The use ofvarious compounds containing an aromatic residue such as, inter alia,3-amino-2-carboxy-4-chlorobenzophenone to provide improved adhesionbetween rubber and brass is disclosed in EP 0137987. The use of anaromatic triazole to improve the adhesion of rubber to a brass-coatedsteel tire cord is described in GB 2032807, U.S. Pat. No. 4,169,112 andU.S. Pat. No. 4,283,460. In many cases the compound used to promoteadhesion is incorporated into a rubber formulation containingconventional additives such as, for example, filler, curing agent andcure accelerator. However, U.S. Pat. No. 4,283,460 discloses adding theadhesion promoter to the rubber adjacent to the tire cord. U.S. Pat. No.4,299,640 and GB 2037617 disclose processes in which the tire cord iscoated with at least one adhesion promoter before being combined withthe vulcanisable rubber composition.

We have now found a class of compound, the members of which haveproperties which are particularly useful in systems in which a metal isin contact with rubber.

According to the present invention there is provided a compound whichcontains a ligand group and a group of the formula

    --XR.sub.n

where

X is a linking group which contains at least one hetero-atom;

R is a hydrocarbyl group which is either a saturated hydrocarbyl groupcontaining at least six carbon atoms or an unsaturated hydrocarbyl grouphaving a chain length of at least three carbon atoms; and

n is an integer which has a value of at least one.

The valency of the group X is equal to (n+1), and hence is at least two.Typically the value of n is one up to four and hence the valency of X istypically two up to five. The hetero-atom in the group X is a connectingatom between the group R and the ligand group and is any atom other thana carbon or hydrogen atom. The group X may be only the hetero-atom ormay contain at least one atom other than the hetero-atom. Typically, thegroup X contains more than the hetero-atom and may contain severalhetero-atoms. The hetero-atom which is present in the group X may be anyhetero-atom of the type which is to be found in an organic compound andmay be a sulphur atom but typically is a nitrogen or oxygen atom. Thenitrogen may be present as a group --NR¹ -- where R¹ is a hydrogen atomor a hydrocarbyl group, typically a lower alkyl group, that is onecontaining not more than five carbon atoms. The group X may be a group--NR¹ --, but in general is a group --COO-- or --NR¹ CO or a morecomplex group which contains more than one hetero-atom as a connectingatom between the group R and the ligand group. Complex groups which canform the group X include groups in which two or more hetero-atoms, forexample nitrogen atoms, are linked by connecting atoms which may be astraight or branched chain or a ring system. Complex groups of this typetypically include a ring system which is either a hydrocarbon ring or aheterocyclic ring particularly a heterocyclic ring in which at least oneof the hetero-atoms is a nitrogen atom. If the group X contains ahydrocarbon ring this may be an aromatic ring, for example a1,4-phenylene group as in a --NH--C₆ H₄ --NHCO-- group. Heterocyclicrings which may be present in the group X include pyridine, pyrazine,pyrimidine, and triazine rings, and these heterocyclic rings may containtwo or more hetero-atom substituent groups. Thus, the group X may bederived from a substituted triazine compound wherein the substituentgroups each contain at least one hetero-atom, for example as intriaminotriazine. If the group X is derived from triaminotriazine, oneof the amine groups is connected to the ligand group and one or both ofthe remaining amine groups is connected to one or more of the groups R.Thus, if the group X is derived from a triaminotriazine group, there maybe up to four groups R connected to the group X, for example as in thegroups --NH--TAZ(NR₂)₂ and --NH--TAZ(NHR)₂ where TAZ represents atriazine ring, particularly a 1,3,5-triazine ring.

The group R is a hydrocarbyl group and may be saturated or unsaturated.If the group R is a saturated hydrocarbyl group, preferably it is agroup having a chain length of at least six carbon atoms. The group Rmay be a straight chain or branched group and is conveniently a straightchain group. The group R contains at least three or six carbon atomsdepending on whether it is an unsaturated or saturated grouprespectively. In general the group R contains not more than 30 carbonatoms, typically not more than 24 carbon atoms, for example up to 18carbon atoms. If the group R is a saturated hydrocarbyl group ittypically contains at least 8 carbon atoms. If the group R is anunsaturated hydrocarbyl group, there may be more than one unsaturatedbond present. The unsaturated bond is preferably a double bond. If thegroup R contains two or more double bonds, the double bonds may beconjugated or non-conjugated or, if there are sufficient double bonds,there may be a combination of both conjugated or non-conjugated doublebonds present in the group R. Typically the group R, when unsaturated,contains one or two double bonds. If the group R is an unsaturatedhydrocarbyl group, it is typically of the general type

    --R.sup.2 CH═CHR.sup.3

where

R² is a divalent hydrocarbyl group; and

R³ is a hydrogen atom or a monovalent hydrocarbyl group.

The group R² contains at least one carbon atom and may be a methylene(--CH₂ --) group or may be a saturated or unsaturated group containingat least two carbon atoms such as, for example, a heptylene group (--C₇H₁₄ --), an octylene group (--C₈ H₁₆ --), a vinylene group (--CH═CH--),a propylene group (--CH₂ --CH═CH--) or a dec-2-enylene group (--C₇ H₁₄CH═CHCH₂ --). The group R³ may be a hydrogen atom or a monovalenthydrocarbyl group, particularly an alkyl group containing up to tencarbon atoms, for example a methyl, pentyl, octyl or decyl group.Examples of the group R include octyl, octadecyl, allyl, decenyl,heptadecenyl, penta-1,3-dienyl, hexa-2,4-dienyl andheptadeca-8,11-dienyl groups.

The ligand group preferably contains at least two hetero-atoms. Thehetero-atom can be, for example, a nitrogen, sulphur or oxygen atom.Many suitable ligand groups contain at least one of the hetero-atoms ina ring system. The ligand group may be a triazole, an imidazole, anindazole, a thiazole, an oxazole, a carbamate, a xanthate or aphthalazine group or a derivative thereof. Derivatives of the ligandgroup include benzotriazole, naphthotriazole, benzimidazole,naphthimidazole, 2-mercaptothiazole, 2-mercaptobenzothiazole,2-mercaptobenzimidazole, 2-mercaptobenzoxazole and carbamate derivativessuch as dithiocarbamates. The ligand group may be a substituted triazinegroup such as 1,3,5-triazine-2,4-dithiol. An alternative ligand group isa trihydroxybenzene group, particularly a 1,2,3-trihydroxybenzene group.

It will be appreciated that the group --X(R)_(n) is separate from theligand group and together the two groups form the compounds of thepresent invention. The group --X(R)_(n) may be bonded to one of thehetero-atoms of the ligand group, but is preferably bonded to a carbonatom of the ligand group. Preferred compounds for use in the process ofthe present invention are those in which the ligand group is a part of afused ring system, for example as in benzotriazole,mercaptobenzothiazole and the like, and the group --X(R)_(n) is bondedto one of the carbon atoms of the benzo group, for example as in a5-substituted benzotriazole, a 4-substituted naphthotriazole or a6-substituted-2-mercaptobenzothiazole.

In the compounds of the present invention the group, or groups, R islinked to the ligand group through the group X which may be, or mayinclude, an amino, an amido, or a carbonyloxy (ester) group or aheterocyclic ring such as is present in a triazinyl group.

Compounds in which R is linked to the ligand group through an amidogroup (--NHCO--) include

5(hexa-2,4-dienoylamino)-benzotriazole;

6(hexa-2,4-dienoylamino)-2-mercaptobenzothiazole;

5(octadeca-9,12-dienoylamino)-benzotriazole;

6(octadeca-9,12-dienoylamino)-2-mercaptobenzothiazole;

5(octadec-9-enoylamino)-benzotriazole;

6(octadec-9-enoylamino)-2-mercaptobenzothiazole;

5(undec-10-enoylamino)-benzotriazole; and

6(undec-10-enoylamino)-2-mercaptobenzothiazole.

Compounds in which R groups are linked to the ligand group through aheterocyclic ring include those in which the ring is a triazine ring asin an aminotriazinyl group. Compounds in which the linking group is anaminotriazinyl group contain groups such as --NH--TAZ(NHR)₂ and--NH--TAZ(NR₂)₂ and include

5(2,4-bis(allylamino)-s-triazin-6-ylamino)-benzotriazole;

6(2,4-bis(allylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole;

6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole;

5(2,4-bis(diallylamino)-s-triazin-6-ylamino)-benzotriazole;

5(2,4-bis(n-octadecylamino)-s-triazin-6-ylamino)-benzotriazole;

5(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)-benzotriazole;

6(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole.

Compounds in which R is linked to the ligand group through a carbonyloxy(ester) group include

5-allyloxycarbonylbenzotriazole;

3,4,5-trihydroxyallylbenzoate; and

3,4,5-trihydroxy(hexa-2,4-dien-1-yl)benzoate.

Other compounds in accordance with the present invention in which thegroup linking R to the ligand group is different from the linking groupin the foregoing compounds include

2,4-dithiol-6(4-(hexa-2,4-dienoylamino)phenyl)amino-s-triazine

in which the ligand group is the 2,4-dithiol-s-triazine group and thelinking group is a 4-amidoanilino group.

The compounds of the present invention can be prepared by the use ofknown reaction processes and reaction conditions. The appropriateprocess and conditions required depend on the type of compound beingprepared, in particular the nature of the linking group X, and may alsodepend on the nature, and amounts, of the group R. Thus, it has beenfound that in the preparation of analogous compounds in one of which thegroup R has a longer hydrocarbon chain, the preparation of the compoundin which R has a longer hydrocarbon chain may require the use of ahigher reaction temperature but a higher temperature is not alwaysnecessary.

The compounds of the present invention may be prepared using, forexample, amine, carboxylic acid, hydroxy, hydroxyalkyl, thiol oralkylthiol derivatives of the ligand group. The compounds of the presentinvention are conveniently prepared using an amine or carboxylic acidderivative of the ligand group, for example 5-aminobenzotriazole,6-amino-2-mercaptobenzo-thiazole, 5-carboxybenzotriazole or3,4,5-trihydroxybenzoic acid. The ligand derivative may be reacted undersuitable conditions with an acid, acid chloride, alcohol, thiol or aminecontaining the group R to form the linking group X, for example an amidoor ester link.

If the linking group is more complex, for example one including atriazine group, the compound of the present invention may be prepared bya two stage process in which the ligand derivative is reacted with abridging compound and the intermediate product is then reacted with asuitable compound containing at least one R group, for example an amineof the type RNH₂ or R₂ NH. The bridging compound is a compoundcontaining at least two substituents, one of which is reactive with theligand derivative and at least one of which is reactive with thecompound containing at least one R group. Cyanuric chloride can be usedas the bridging compound to obtain a compound in which the linking groupcontains a triazine group.

Compounds of the present invention in which the linking group is anamido group (--NHCO--) are conveniently prepared by the reaction of anamino-substituted derivative of the ligand group with an acid chlorideof the type RCOCl. The reaction is conveniently effected in a polarsolvent such as aqueous acetone. The reaction is typically effected inthe presence of a base, for example sodium bicarbonate, sodium acetateor sodium hydroxide. In general this reaction can be effected withoutheating and it may be preferred to cool the reaction mixture to effectthe reaction at a temperature which is typically in the range from 0° to20° C.

Compounds of the present invention in which the linking group is anester, that is carbonyloxy, group (--COO--) are conveniently prepared bythe reaction of a carboxylic acid derivative of the ligand group with analcohol of the type ROH. Other procedures for the preparation of estersmay be used but the reaction between an acid and an alcohol is aparticularly convenient procedure. The process for the preparation ofsuch compounds is an esterification process and is effected under knownesterification conditions. Thus, the esterification process is typicallyeffected at an elevated temperature which is typically at least 40° C.and may be as high as 300° C. In general esterification temperatures inexcess of about 150° C. are required only for the preparation ofcompounds of high molecular weight, particularly for the preparation ofsome polyesters, that is compounds containing at least two ester groups.Generally a reaction temperature of at least 60° C. is desired, forexample a temperature in the range from 80° C. to 120° C. The reactionis conveniently effected in the liquid phase and may be effected usingan excess of one of the reactants, particularly an excess of thealcohol, as the solvent for the reaction. We have found that if thealcohol is a dienol, for example hexa-2,4-dien-1-ol, polymerisation ofthe dienyl group may occur under the esterification conditions to form apolymeric material.

Thus, according to a further aspect of the present invention there isprovided a polymeric material which is the product of esterifying acarboxylic acid with an alcohol which is, or an alcohol mixture whichincludes, a dienol. More specifically, the polymeric material is theproduct of esterifying a carboxylic acid with a stoichiometric excess ofa dienol.

According to a specific embodiment of this further aspect of the presentinvention the polymeric material is the product of esterifying3,4,5-trihydroxybenzoic acid with a stoichiometric excess of a dienolsuch as, for example hexa-2,4-dien-1-ol. The product obtained isessentially free of carboxylic acid groups and is believed to be apolymer of 3,4,5-trihydroxy(hexa-2,4-dien-1-yl) benzoate andhexa-2,4-dien-1-ol.

The esterification is effected under conventional esterificationconditions including the presence of a catalyst such as, for example,toluene-4-sulphonyl chloride, toluene-4-sulphonic acid and concentratedsulphuric acid. We have obtained satisfactory products usingtoluene-4-sulphonic acid as the esterification catalyst.

Compounds in which the linking group X is more complex than amido orester groups include compounds containing more than one group R and inwhich the group X is more than a divalent group. In such compounds thegroup X may be, for example, a substituted triazine group, moreparticularly a triazine group containing more than one substituent groupcontaining a hetero-atom especially as in a polyaminotriazine group. Asnoted previously herein, such compounds are typically prepared in atleast two stages in the first of which a ligand compound having at leastone substituent containing a hetero-atom is reacted with a bridgingcompound which conveniently is cyanuric chloride, and the reactionproduct is then reacted with a compound containing at least one group R,for example a compound containing a replaceable hydrogen atom, ahetero-atom and at least one group R, such as an amine compound of thetype RNH₂ or R₂ NH.

The reaction of the hetero-group substituted ligand with cyanuricchloride may be effected in solution in a suitable solvent for example apolar solvent such as acetone or aqueous acetone. The reaction istypically effected in the presence of a base such as sodium bicarbonate.The reaction can be effected without the application of heat and it isgenerally preferred that the reaction mixture is cooled to maintain thetemperature below ambient temperature and particularly to maintain atemperature of not more than 10° C., for example at 0° to 5° C.

The product obtained by the foregoing reaction is an intermediateproduct which contains a dichlorotriazine group linked to the ligandgroup through a hetero-atom, for example as in a dichlorotriazine aminosubstituted derivative of the ligand group. The intermediate product isthen reacted with an appropriate compound such as an amine to obtain acompound in accordance with the present invention. If this subsequentreaction is effected using an amine, it is conveniently effected in theabsence of a solvent using a stoichiometric excess of the amine as thereaction medium. The reaction may, if desired, be effected in thepresence of a suitable inert solvent such as, for example acetone orbutanone, but the presence of a solvent is not necessary. If the amine,or other reactant, is one containing an unsaturated group, a phenol ispreferably present in the reaction mixture to act as a polymerisationinhibitor. A suitable phenol is 2,4,6-tri-t-butylphenol. The reactionwith the amine may be effected at any suitable temperature which may befrom 0° C. up to about 120° C., depending particularly on the amineused. Thus, using a lower amine, for example allylamine or diallylamine,the reaction may be effected at a temperature of not more than about 40°C., for example by cooling the reaction mixture to prevent anundesirably high temperature from being attained. Using a higher amine,for example di-n-octylamine or n-octadecylamine, a higher reactiontemperature of at least 60° C. is desirable.

If the linking group is an amidoanilino group for example as in2,4-dithiol-6(4(hex-2,4-dienoylamino)phenyl)amino-s-triazine, thepreparation of this may require three reaction stages. Thus, thecompound containing the ligand group may be reacted with nitroaniline,the nitro group in the resulting compound reduced to an amine group andthis reacted with an acid halide to obtain the desired product.

More specifically, nitroaniline is reacted with cyanuric chloride inessentially equimolar proportions to form2,4-dichloro-6-(4-nitrophenyl)amino-s-triazine. The reaction isconveniently effected in a polar liquid medium which is a solvent ordispersing medium for the reactants and the reaction product, a suitableliquid medium being aqueous acetone. The reaction is preferably effectedat a temperature below ambient temperature, for example from 0° C. up to20° C., typically less than 5° C. The reaction mixture is maintainedessentially neutral by the addition of a base, for example sodiumcarbonate, during the reaction.

The intermediate product obtained is then reacted with sodium hydrogensulphide. The reaction is conveniently effected in water and is effectedat an elevated temperature which is at least 60° C. up to 120° C. and isconveniently at the reflux temperature of the reaction mixture. Underthe reaction conditions, the chlorine is replaced by thiol groups (--SH)and the nitro group is reduced to give an amino group.

The second intermediate product thus obtained is the ligand derivativewhich is then reacted with an acid chloride to obtain the desiredproduct. The reaction of this ligand derivative with the acid chlorideis conveniently effected using reaction conditions similar to thosedescribed previously herein for the preparation of compounds in whichthe linking group X is an amido group.

The compounds of the present invention, and any intermediate materialsif desired, may be purified using appropriate techniques known for thispurpose such as extraction with suitable liquids which are solventseither for the desired product or impurities. The product may becrystallised from suitable solvents or may be thoroughly washed usingone or more liquids to remove undesired impurities.

The compounds of the present invention are effective to reduce corrosionof metals or to improve the adhesion of a metal to another material orto both reduce corrosion and improve adhesion. The preferred compound isdependent on the nature of the ligand group, the nature of the group--XR_(n) and the metal. Thus, if the ligand group is a benzotriazolegroup, the metal is preferably copper, if the ligand group is amercapto-benzothiazole group the metal is preferably zinc and if theligand is a 1,2,3-trihydroxyphenyl group the metal is preferably iron orsteel.

The compounds of the present invention may be used in composites of ametal and a non-metallic material, for example a polymeric material suchas rubber. The metal may be a reinforcement for the non-metallicmaterial, for example rubber reinforced with a metal as in powertransmission belts, conveyor belts, rubber hoses and metal reinforcedtires.

Thus, a particular embodiment of the present invention comprises acomposite which is metal reinforced rubber which also includes at leastone compound in accordance with the first aspect of the presentinvention.

The composite is, in particular, in the form of a tire reinforced withmetal tire cords.

When the metal reinforcement is a tire cord it is typically formed ofsteel or brass-coated steel.

The composite may include more than one compound in accordance with thepresent invention. It is preferable to use more than one compound if themetal is an alloy and the compounds then very preferably containdifferent ligand groups. Thus, if the metal is a brass-coated steel tirecord, there may be present three different compounds in each of whichthere is a different ligand group, particularly compounds in which theligand groups are benzotriazole, mercaptobenzothiazole and1,2,3-trihydroxybenzene. The compounds are used in proportions dependingon the composition of the brass coating and also the completeness ofcoating of the steel cord. A typical mixture of compounds would be suchas to provide from 5 up to 95%, especially 30-60%, molar ofbenzotriazole ligand groups, from 5 up to 95%, especially 30-60%, molarof mercaptobenzothiazole ligand groups and from 1 up to 90%, especially5-30%, molar of 1,2,3-trihydroxybenzene ligand groups, the % molar ofligand groups totalling 100%.

The rubber may be natural or synthetic rubber and may be formulated withvarious additives of the type known in the rubber compounding art.

As noted previously herein, the preferred compound is dependent on thenature of the group --XR_(n). When used in metal reinforced rubber, itis preferred that the group R is an unsaturated hydrocarbyl group. Wehave found that better effects are generally obtained when the group Rcontains not more than 12 carbon atoms. If the group X is a group--COO-- or --NHCO--, the group R may be an unsaturated group containing3 to 12 carbon atoms and the value of n is one whereas if X is anamino-substituted triazine group, the group R is conveniently anunsaturated group containing 3 to 6 carbon atoms and the value of n isat least two and may be four.

If the metal is brass-coated steel, when using a single compound we haveobtained particularly useful results using compounds in which the ligandgroup is a 2-mercaptobenzothiazole group.

A particularly useful type of compound in accordance with the presentinvention is one in which the ligand group is mercaptobenzothiazole,especially 2-mercaptobenzothiazole, the group X is --COO-- or --NHCO--,or an amino-substituted triazine, the group R is an unsaturated groupcontaining 3 to 12 carbon atoms and the value of n is one when X is--COO-- or --NHCO-- and the value of n is at least two up to four when Xis an amino-substituted triazine group. Compounds of the foregoing typeinclude

6(hexa-2,4-dienoylamino)-2-mercaptobenzothiazole;

6(undec-10-enoylamino)-2-mercaptobenzothiazole;

6(2,4-bis(allylamino)-s-triazine-6-ylamino)-2-mercaptobenzothiazole; and

6(2,4-bis(diallylamino)-s-triazine-6-ylamino)-2-mercaptobenzothiazole.

Especially useful results have been obtained using compounds in whichthe group X is an amino-substituted triazine group.

The compounds of the present invention may be incorporated into therubber formulation, for example as is disclosed in GB 2032807, U.S. Pat.No. 4,169,112 and U.S. Pat. No. 4,283,460. Alternatively, the compoundsof the present invention may be incorporated only into a part of therubber formulation, this part of the rubber formulation being thatadjacent to the metal, as is disclosed in U.S. Pat. No. 4,283,460. As ayet further alternative, the compounds of the present invention may beapplied to the metal, as is disclosed in U.S. Pat. No. 4,299,640 and GB2037617. It will be appreciated that the foregoing procedures may becombined and one or more compounds in accordance with the presentinvention may be applied to the metal and one or more compounds inaccordance with the present invention incorporated into the rubber whichis to be applied to the metal, and the compound, or compounds, on themetal and in the rubber may be the same or different.

In order that the various embodiments of the present invention are morereadily appreciated, various aspects thereof are described in thefollowing, non-limiting examples in which parts are by weight unlessspecified to the contrary.

EXAMPLE 1

(A) Preparation of hexa-2,4-dienoyl chloride

11.2 parts of hexa-2,4-dienoic acid (sorbic acid, obtained from AldrichChemical Co. Ltd.) were stirred with 60 parts of toluene containing 1part of dimethylformamide and 0.2 parts of 2,4,6-tri-t-butylphenol. Themixture was heated to 75° C. Complete solution was observed when thetemperature reached 40° C. A solution containing 13.5 parts of thionylchloride dissolved in 30 parts of toluene was then added dropwise to thehot solution of hexa-2,4-dienoic acid over a period of 1.5 hours,maintaining the internal temperature at 75°-80° C. A pale brown solutionwas obtained and this was stirred for a further one hour. The toluenewas then removed by distillation under reduced pressure. (20-25 Torr),and a temperature of 65°-70° C. Distillation was continued at 15-18Torr, and 80°-82° C. 9.0 parts (69% yield based on the acid) of a paleyellow distillate were collected.

By analysis the product was found to contain C 55.1% wt %; H 5.4% wt;and Cl 27.1% wt. Hexa-2,4-dienoyl chloride (C₆ H₇ ClO) requires C 55.2%wt; H 5.36% wt; and Cl 27.2% wt.

(B) Preparation of 5(hexa-2,4-dienoylamino)benzotriazole

A mixture of 2.68 parts of 5-aminobenzotriazole, prepared as describedin U.S. Pat. No. 4,428,987, 25 parts of water and 100 parts of acetonewas warmed to 40° C. to effect a complete solution. To this solution wasthen added a suspension containing 2.5 parts of sodium bicarbonate in 20parts of water. The resulting mixture was stirred and cooled to 5°-10°C. in a cooling bath containing ice and water. A solution containing 3.0parts of hexa-2,4-dienoyl chloride (prepared as described in A)dissolved in 20 parts of acetone was added dropwise to the reactionmixture over 30 minutes, maintaining an internal temperature of between5° and 10° C. throughout the addition. A further charge of 1.5 parts ofhexa-2,4-dienoyl chloride dissolved in 10 parts of acetone was addedover 15 minutes, and stirring was continued at between 5° and 10° C. forone hour. A solution containing 5 parts of sodium bicarbonate dissolvedin 150 parts of water was then added, and the reaction mixture stirredfor two hours, allowing the internal temperature to rise to between 20°and 25° C. A pale cream solid (2.75 parts, melting point 215°-217° C.,58.3% yield) was isolated by filtration, washed with water and dried atreduced pressure (18-22 Torr) at 20° C. for 24 hours.

By analysis the product was found to contain C 61.0% wt; H 5.2% wt; N23.6% wt. The compound 5(hexa-2,4-dienoylamino)benzotriazole (C₁₂ H₁₂ N₄O) requires C 63.2% wt; H 5.3% wt; N 24.6% wt.

EXAMPLE 2

(A) Preparation of 6-amino-2-mercaptobenzothiazole

A solution containing 100 parts of 2-mercaptobenzothiazole dissolved in146 parts of concentrated sulphuric acid (SG 1.84) was cooled to 0°-2°C. The solution was treated with a mixture of 37 parts of fuming nitricacid (SG 1.5) and 30 parts of sulphuric acid (SG 1.84) over 3.5 hours,maintaining the internal temperature of the mixture at 0°-5° C. Themixture was allowed to warm to 20°-25° C. and stirred for a further 16hours. The yellow solution was then poured carefully into 1000 parts ofcrushed ice which was being stirred. A pale yellow precipitate wasformed which was isolated by filtration and washed well with cold water.The yellow filtercake was dissolved in 1000 parts of water andsufficient 10N aqueous sodium hydroxide solution to raise the pH of thesolution to between 11 and 12. This solution was filtered and acidified,with stirring, to a pH in the range 2 to 3 by the addition ofconcentrated hydrochloric acid. A bright yellow precipitate (113 parts)was formed which was isolated by filtration and dried at 60° C. for 48hours.

132 Parts of sodium hydrogen sulphide was dissolved in 400 parts ofwater, and stirred at 20° C. 53 Parts of6-nitro-2-mercaptobenzothiazole, prepared as described previouslyherein, was added over 10 minutes; the reaction mixture was then heatedto 110° C., and stirred whilst boiling the mixture under refluxconditions. After four hours boiling, the mixture was cooled to between0° and 5° C. and stirred for one hour. The product,6-amino-2-mercaptobenzothiazole (30.3 parts), was isolated byfiltration, washed sparingly with cold water and dried at 60° C. for 24hours.

(B) Preparation of 6(hexa-2,4-dienoylamino)-2-mercaptobenzothiazole

3.60 Parts of 6-amino-2-mercaptobenzothiazole (prepared as described inA) were reacted with hexa-2,4-dienoyl chloride (prepared as described inpart A of Example 1) using the procedure described in part B of Example1.

By analysis, the product obtained (1.45 parts, melting point 264°-266°C., 26% yield) was found to contain C 55.8% wt; H 4.4% wt; N 9.7% wt;and S 22.0% wt. 6(hexa-2,4-dienoylamino)-2-mercaptobenzothiazole (C₁₃H₁₂ N₂ S₂ O) requires C 56.5% wt; H 4.3% wt; N 10.1% wt; and S 23.7% wt.

EXAMPLE 3

(A) Preparation of Octadeca-9,12-dienoyl chloride

27.5 Parts of octadeca-9,12-dienoic acid (linoleic acid) were stirredwith 50 parts of toluene and 0.5 parts of dimethyl formamide. Thesolution was heated to 75° C. and 15 parts of thionyl chloride dissolvedin 50 parts of toluene were added slowly over 1.5 hours whilstmaintaining the reaction temperature at 75°-80° C. After a further 2.5hours, the toluene was removed by distillation under reduced pressure(20-25 Torr) and a temperature of 70°-80° C. and then the product (20.0parts; 67.9% yield) was obtained by distillation at 0.1 Torr and atemperature of 160°-170° C.

By analysis the product was found to contain C 72.0% wt; H 10.3% wt; andCl 11.8% wt. Octadeca-9,12-dienoyl chloride (C₁₈ H₃₁ ClO) requires C72.4% wt; H 10.4% wt; and Cl 11.9% wt.

(B) Preparation of 5(octadeca-9,12-dienoylamino)-benzotriazole

13.4 Parts of 5-aminobenzotriazole, prepared as described in U.S. Pat.No. 4,428,987, 200 parts of water, 10 parts of sodium bicarbonate and100 parts of acetone were stirred together and cooled to 5° C. byimmersion in an ice-bath.

A solution containing 39 parts of octadeca-9,12-dienoyl chloride(prepared as described in A) and 30 parts of acetone was added to thestirred reaction mixture over one hour, maintaining the temperaturebelow 10° C. throughout the addition. After stirring for a further threehours whilst allowing the temperature to rise to 20° C., 15 parts of 10Naqueous sodium hydroxide were added, and the mixture was stirred at 20°C. for 16 hours. 10 Parts of glacial acetic acid were then added, andthe reaction mixture was filtered. The collected solid was washed wellwith water (about 20° C.) and dried at 60° C. for 16 hours. A slightlysticky solid was obtained and this was stirred in 200 parts ofchloroform at 20° C. for 5 hours. The solid product (18.3 parts, meltingpoint 169°-171° C., 46.2% yield) was isolated by filtration, washed withchloroform, and dried at 60° C. for 16 hours.

By analysis the product was found to contain C 70.3% wt; H 9.3% wt; andN 13.4% wt. 5(octadeca-9,12-dienoylamino)benzotriazole (C₂₄ H₃₆ ON₄)requires C 72.7% wt; H 9.1% wt; and N 14.1% wt.

EXAMPLE 4 Preparation of6(octadeca-9,12-dienoylamino)-2-mercaptobenzothiazole

3.6 Parts of 6-amino-2-mercaptobenzothiazole (prepared as described inPart A of Example 2) were stirred with 200 parts of acetone and 50 partsof water. A solution containing 3.2 parts of anhydrous sodium acetatedissolved in 30 parts of water was added, and the mixture cooled tobetween 10° and 15° C. 8 Parts of octadeca-9,12-dienoyl chloride(prepared as described in Part A of Example 3), dissolved in 50 parts ofacetone was added to the stirred reaction mixture over one hour whilstmaintaining the internal temperature at between 10° and 15° C. byimmersion in a bath containing ice and water. The reaction mixture wasstirred for a further four hours at less than 15° C., then 10 parts of a10N aqueous solution of sodium hydroxide were added, and the mixture wasstirred for 16 hours, allowing the temperature to rise to 20° C.

7 Parts of glacial acetic acid were then added, and the mixture wasfiltered. The collected solid was washed with water and dried at 18-25Torr and 20° C. for 24 hours.

The product (5.22 parts, melting point 158°-160° C., 55.8% yield) wasfound by analysis to contain C 64.2% wt; H 8.0% wt; N 5.8% wt; and S13.5% wt. 6(Octadeca-9,12-dienoylamino)-2-mercaptobenzothiazole (C₂₅ H₃₆N₂ S₂ O) requires C 67.6% wt; H 8.1% wt; N 6.3% wt; and S 14.4% wt.

EXAMPLE 5

(A) Preparation of Octadec-9-enoyl chloride

Octadec-9-enoyl chloride (25.5 parts, boiling point 160°-180° C. at 0.12Torr, 85% yield) was prepared from 28.1 parts of octadec-9-enoic acidusing the procedure described in part A of Example 3 for the preparationof octadec-9,12-dienoyl chloride.

(B) Preparation of 5(octadec-9-enoylamino)benzotriazole

2.68 Parts of 5-aminobenzotriazole (prepared as described in U.S. Pat.No. 4,428,987) were reacted with 7.0 parts of octadec-9-enoyl chloride(prepared as described in A) using the procedure described in part B ofExample 3 for the preparation of5(octadeca-9,12-dienoylamino)-benzotriazole.

The product (2.4 parts, melting point 180°-181° C., 29.6% yield) wasfound by analysis to contain C 70.8% wt; H 10.0% wt; and N 14.0% wt.5(Octadec-9-enoylamino) benzotriazole (C₂₄ H₃₈ N₄ O) requires C 72.4%wt; H 9.5% wt; and N 14.1% wt.

EXAMPLE 6 Preparation of 6(octadec-9-enoylamino)-2-mercaptobenzothiazole

3.6 Parts of 6-amino-2-mecrcaptobenzothiazole (prepared as described inpart A of Example 2) were reacted with 7.8 parts of octadec-9-enoylchloride (prepared as described in part A of Example 5) using theprocedure described in Example 4 for the preparation of6(octadeca-9,12-dienoylamino)-2-mercaptobenzothiazole.

The product (3.60 parts, melting point 154°-156° C., 40.8% yield) wasfound by analysis to contain C 66.9% wt; H 8.9% wt; N 6.1% wt; and S14.3% wt. 6(octadec-9-enoylamino)-2-mercaptobenzothiazole (C₂₅ H₃₈ N₂ S₂O) requires C 67.3% wt; H 8.5% wt; N 6.3% wt; and S 14.3% wt.

EXAMPLE 7

(A) Preparation of undec-10-enoyl chloride

Undec-10-enoyl chloride (12 parts, boiling point 80°-84° C. at 0.16Torr, 59.25% yield) was prepared from 18.4 parts of undec-10-enoic acid(obtained from Aldrich Chemical Co. Ltd.) using the procedure describedin part A of Example 3.

(B) Preparation of 5(undec-10-enoylamino)-benzotriazole

2.68 Parts of 5-aminobenzotriazole (prepared as described in U.S. Pat.No. 4,428,987) were reacted wiht 7.56 parts of undec-10-enoyl chloride(prepared as described in part A), using the procedure described inExample 4 for the preparation of6(octadec-9,12-dienoylamino)-2-meraaptobenzothiazole.

The product (4.5 parts, melting point 189°-191° C., 73.3% yield) wasfound by analysis to contain C 66.5% wt; H 8.4% wt; and N 17.8% wt.5(undec-10-enoylamino)-benzotriazole (C₁₇ H₂₄ N₄ O) requires C 68% wt; H8.0% wt; and N 18.7% wt.

EXAMPLE 8 Preparation of 6(undec-10-enoylamino)-2-mercaptobenzothiazole

3.6 Parts of 6-amino-2-mercaptobenzothiazole (prepared as described inpart A of Example 2) were reacted with 5.1 parts of undec-10-enoylchloride (prepared as described in part A of Example 7) using theprocedure described in Example 4 for the preparation of6(octadec-9,12-dienoylamino)-2-mercaptobenzothiazole.

The product (4.15 parts, melting point 140°-142° C., 58.5% yield) wasfound by analysis to contain C 60.8% wt; H 7.0% wt; N 7.8% wt; and S18.4% wt. 6(undec-10-enoylamino)-2-mercaptobenzothiazole (C₁₈ H₂₄ N₂ S₂O) requires C 62.1% wt; H 6.9% wt; N 8.0% wt; and S 18.4% wt.

EXAMPLE 9

(A) Preparation of 5(2,4-dichloro-s-triazin-6-ylamino)benzotriazole

21.44 Parts of 5-aminobenzotriazole (prepared as described in U.S. Pat.No. 4,428,987) and 280 parts of acetone were warmed to 40° C. to effecta complete solution. After cooling to below 10° C. this solution wasadded to a stirred solution containing 28.8 parts of cyanuric chloridedissolved in 200 parts of acetone. The reaction mixture was stirred atbetween 0° and 5° C. and a solution containing 13.6 parts of sodiumbicarbonate in 200 parts of water was added dropwise over one hourwhilst maintaining the internal temperature at between 0° C. and 5° C.by means of an external ice-bath. The reaction mixture was then stirredat between 0° and 5° C. for a further two hours. A pale cream solid(43.6 parts, 96% yield) was isolated by filtration, washed well withcold water, and dried at 18-25 Torr and 20° C. for 48 hours.

By analysis the product was found to contain C 38.0% wt; H 2.3% wt; N33.7% wt; and Cl 24.3% wt.5(2,4-dichloro-s-triazin-6-ylamino)-benzotriazole (C₉ H₅ N₇ Cl₂)requires C 38.3% wt; H 1.77% wt; N 34.8% wt; and Cl 25.2% wt.

(B) Preparation of5(2,4-bis(allylamino)-s-triazin-6-ylamino)benzotriazole

10 Parts of allylamine and 0.1 parts of 2,4,6-tri-t-butylphenol werestirred together at 20°C. 4.5 parts of5-(2,4-dichloro-s-triazin-6-ylamino)benzotriazole (prepared as describedin part A) were added in small portions over 30 minutes. The temperaturewas maintained at between 30° and 35° C. by cooling the reaction mixtureexternally in a water bath (temperature of bath 20°±2° C.). Theresulting mixture was stirred at between 20° and 25° C. for 16 hours.100 parts of cold water (20° C.) were then added, and a pale yellowsolid was isolated by filtration, and washed with water. The filter cakeso obtained (4.8 parts) was stirred with 150 parts of water. Thismixture was treated with 1.5 parts of sodium hydroxide pellets, andstirred for ten minutes. 0.5 Parts of decolourising charcoal (CarbonDY3) were added, and stirring was continued, at 20° C., for a further 30minutes. The mixture was filtered, and the filtrates were acidified with3 parts of glacial acetic acid. The product (2.6 parts, melting point100°-104° C., 49.3% yield) was isolated by filtration, washed with waterand dried at 18-25 Torr and 20° C. for 24 hours.

By analysis the product was found to contain C 54.1% wt; H 5.4% wt; andN 36.5% wt. The compound5(2,4-bis(allylamino)-s-triazin-6-ylamino)benzotriazole (C₁₅ H₁₇ N₉)requires C 55.7% wt; H 5.3% wt; and N 39% wt.

EXAMPLE 10

(A) Preparation of6(2,4-dichloro-s-triazin-6-ylamino)-2-mercaptobenzothiazole

14.4 Parts of 6-amino-2-mercaptobenzothiazole (prepared as described inpart A of Example 2) were reacted with 14.4 parts of cyanuric chlorideusing the procedure described in part A of Example 9.

By analysis the product obtained (22.3 parts, 70% yield) was found tocontain C 34.7% wt; H 1.6% wt; N 20.0% wt; Cl 20.0% wt; and S 19.5% wt.6(2,4-dichloro-s-triazin-6-ylamino)-2-mercaptobenzothiazole (C₁₀ H₅ N₅Cl₂ S₂) requires C 36.4% wt; H 1.5% wt; N 21.2% wt; Cl 21.5% wt; and S19.4% wt.

(B) Preparation of6(2,4-bis(allylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole

5.3 Parts of 6(2,4-dichloro-s-triazin-6-ylamino)-2-mercaptobenzothiazole(prepared as described in part A) were added in small portions to astirred mixture of 10 parts of allylamine and 0.1 parts of2,4,6-tri-t-butylphenol whilst maintaining the temperature of thereaction mixture at between 25° and 30° C. by immersion in a bathcontaining cold water (20°±2° C.). After stirring at 20° C. for afurther 16 hours, the reaction mixture was poured into 200 parts of coldwater (20° C.). An oily insoluble material was formed which wasseparated from the water and dissolved in 100 parts of chloroform. Thechloroform solution was washed with 20 parts of an aqueous Nhydrochloric acid solution, and the layers were separated. Thechloroform solution was dried over anhydrous magnesium sulphate and thenevaporated to dryness. A sticky solid was produced which was stirred in100 parts of hexane for 16 hours, and the solid (2.10 parts, meltingpoint 216°-220° C., 36.1% yield) was isolated by filtration, washed withhexane, and dried at 18-25 Torr and 20° C. for 24 hours.

By analysis this product was found to contain C 50.6% wt; H 4.7% wt; N25.5% wt; and S 16.6% wt.6(2,4-bis(allylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole (C₁₆H₁₇ N₇ S₂) requires C 51.8% wt; H 4.6% wt; N 26.4% wt; and S 17.3% wt.

EXAMPLE 11 Preparation of6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole

11 Parts of diallylamine and 0.1 parts of 2,4,6-tri-t-butylphenol werestirred at 20° C. 5.3 Parts of6(2,4-dichloro-s-triazin-6-ylamino)-2-mercaptobenzothiazole (prepared asdescribed in Part A of Example 10) were added in small portions over 30minutes whilst maintaining the internal temperature at between 30° and35° C. by application of external water cooling. The resultant mixturewas stirred for 16 hours at between 20° and 25° C. 200 Parts ofchloroform were then added, and the resultant dark brown solution waswashed with 200 parts of dilute aqueous hydrochloric acid (0.5M)followed by further washing with 100 parts of dilute sodium chloridesolution (1.0% w/v). The organic solution was then dried over anhydrousmagnesium sulphate, and the chloroform then removed by evaporation. Anoil was obtained and this was stirred with 100 parts of hexane for twohours. A yellow solid (1.9 parts, melting point 160°-161° C., 28.6%yield) was isolated by filtration, washed with hexane and dried at 60°C. for five hours.

By analysis the product was found to contain C 58.1% wt; H 5.5% wt; N21.4% wt; and S 13.8% wt.6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole(C₂₂ H₂₅ N₇ S₂) requires C 58.5% wt; H 5.5% wt; N 21.7% wt; and S 14.2%wt.

EXAMPLE 12 Preparation of5(2,4-bis(diallylamino)-s-triazin-6-ylamino)benzotriazole

4.5 Parts of 5(2,4-dichloro-s-triazin-6-ylamino)benzotriazole (preparedas described in part A of Example 9), were reacted with 12.5 parts ofdiallylamine using the procedure described in Example 11 for thepreparation of6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole.

The product (2.4 parts, melting point 74°-76° C., 37.4% yield) was foundby analysis to contain C 61.3% wt; H 6.0% wt; and N 29.8% wt.5(2,4-bis(diallylamino)-s-triazin-6-ylamino)benzotriazole (C₂₁ H₂₅ N₉)requires C 62.5% wt; H 6.2% wt; and N 31.3% wt.

EXAMPLE 13 Preparation of5(2,4-bis(n-octadecylamino)-s-triazin-2-ylamino)benzotriazole

4.0 Parts of 5(2,4-dichloro-s-triazin-6-ylamino)benzotriazole (preparedas described in part A of Example 9) were added to 25 parts ofn-octadecylamine, and the mixture stirred at between 80° and 90° C. for16 hours. After cooling to 30° C., 200 parts of industrial methylatedspirits were added, followed by 200 parts of hexane. 20 Parts of cupricacetate and a further 200 parts of methylated spirits were then added.After stirring at 20° C. for one hour, the reaction mixture wasfiltered, and the collected solid washed well with methylated spirits.The solid was then stirred with 200 parts of chloroform, and theresultant solution washed with 100 parts of N aqueous hydrochloric acid.This washing procedure was repeated three times. Finally the chloroformsolution was washed with water, dried over anhydrous magnesium sulphate,and evaporated to dryness. The solid thus obtained was stirred with 50parts of methylated spirits for one hour.

The solid (2.30 parts, melting point 84°-86° C., 21% yield) was found byanalysis to contain C 70.7% wt; H 11.1% wt; and N 16.2% wt. The compound5(2,4-di(n-octadecylamino)-s-triazin-6-ylamino)benzotriazole (C₄₅ H₈₁N₉) requires C 72.3% wt; H 10.8% wt; and N 16.9% wt.

EXAMPLE 14 Preparation of5(2,4-bis(di-n-octaylamino)-s-triazin-6-ylamino)benzotriazole

25 Parts of di-n-octylamine were stirred and heated to 75° C. 3.0 Partsof 5(2,4-dichloro-s-triazin-6-ylamino)-benzotriazole (prepared asdescribed in part A of Example 9) were added quickly to the amine. Thereaction mixture was stirred at between 70° and 75° C. for 12 hours,then cooled to 20° C. and poured into 300 parts of industrial methylatedspirits. 10 Parts of cupric acetate were added, and the mixture stirredfor one hour at 20° C. The green crystalline solid which had formed wasfiltered and washed with methylated spirits. The filter cake was thenstirred in 200 parts of ethyl acetate, and 100 parts of aqueous 2Nhydrochloric acid were added. The mixture was stirred vigorously for 20minutes, then transferred to a suitable funnel, where the aqueous andorganic layers disengaged. The lower aqueous layer was discarded, andreplaced with fresh 2N aqueous hydrochloric acid, and the wash processwas repeated. Finally, the ethyl acetate layer was dried over anhydrousmagnesium sulphate, and then the solvent was removed at 18-22 Torr and50°±5° C. An oily product was obtained which was recrystallised from 50parts of boiling methanol, to produce 2.88 parts of a solid product(melting point 78°-80° C., 39.45% yield).

By analysis the product was found to contain C 71.3% wt; H 10.8% wt; andN 18.4% wt. 5(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)benzotriazole(C₄₁ H₇₃ N₉) requires C 71.2% wt;

EXAMPLE 15 Preparation of6(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole

3 Parts of 6(2,4-dichloro-s-triazin-6-ylamino)-2-mercaptobenzothiazole(prepared as described in part A of Example 10) were reacted with 25parts of di-n-octylamine using the procedure described in Example 14 forthe preparation of5(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)benzotriazole. A yield of0.96 parts of product of melting point 81°-83° C. was obtained.

EXAMPLE 16

(A) Preparation of 5-carboxybenzotriazole

45.6 Parts of 3,4-diaminobenzoic acid (obtained from Lancaster SynthesisLtd.) were stirred with 600 parts of water and 60 parts of concentratedaqueous hydrochloric acid of specific gravity 1.18. The reaction mixturewas heated to 60° C., and filtered whilst hot. The filtrates were cooledto below 5° C. by immersing the reaction vessel in a bath containingcrushed ice. 160 Parts of an aqueous 2N solution of sodium nitrite wereadded all at once to the cooled reaction mixture causing the internaltemperature to rise to 22° C. The reaction mixture was then heated to60° C. and stirred at 60° C. for 30 minutes. After cooling to 20° C., asolid product (46.15 parts, 94.4% yield) was isolated by filtration,washed with cold water (20° C.) and dried at 60° C. for 24 hours.

(B) Preparation of 5-allyloxycarbonyl benzotriazole

3.0 Parts of 5-carboxybenzotriazole (prepared as described in A) wereadded to a stirred mixture containing 50 parts of allyl alcohol and 0.2parts of toluene-4-sulphonic acid. The reaction mixture was heated atthe boil (94°-97° C.) under reflux conditions for 24 hours. 0.3 Parts ofconcentrated sulphuric acid were then added and heating at the boilunder reflux was continued for a further 48 hours. The excess allylalcohol was removed by distillation under reduced pressure (20-25 Torr)and at 40°-50° C. and the residual oil was dissolved in 100 parts ofethyl acetate. The ethyl acetate solution was washed with 100 parts ofwater, then dried over anhydrous magnesium sulphate. The ethyl acetatewas then removed by distillation at 18-22 Torr and 50°±5° C., and theresidual solid was stirred in 200 parts of hexane for four hours. Thesolid product (1.15 parts, melting point 95°-97° C., 30.8% yield) wascollected by filtration, washed with hexane and dried at 20-25 Torr and20° C. for 16 hours.

By analysis, the product was found to contain C 58.8% wt; N 20.1% wt;and H 4.6% wt. The compound 5-allyloxycarbonylbenzotriazole (C₁₀ H₉ N₃O₂) requires C 59.1% wt; N 20.7% wt; and H 4.4% wt.

EXAMPLE 17 Preparation of 3,4,5-trihydroxyallylbenzoate

13.6 Parts of 3,4,5-trihydroxybenzoic acid (gallic acid, obtained fromAldrich Chemical Company) were added to 60 parts of allyl alcohol,containing 0.5 parts of 2,4,6-tri-t-butylphenol and 0.4 parts oftoluene-4-sulphonic acid. The mixture was heated at the boil (94°-97°C.) under reflux conditions for 20 hours. A further charge of 0.4 partsof toluene-4-sulphonic acid was added, and boiling under refluxconditions continued for a further 16 hours.

Excess allyl alcohol was then removed under vacuum distillation (20-25Torr) and an internal temperature not exceeding 60° C. The residualsolid was dissolved in 200 parts of ethyl acetate and washed with 100parts of water. After separating the aqueous and organic layers, thelatter was washed with three separate portions of 50 parts of an aqueoussolution containing 1 part of sodium bicarbonate. After drying overanhydrous magnesium sulphate, the ethyl acetate was removed by vacuumdistillation at 18-22 Torr and 50°±5° C. The crude product (11.0 parts)was recrystallised from a mixture containing 90 parts of toluene and 10parts of ethyl acetate, to yield the final product (8.65 parts, meltingpoint 153° C., 51.5% yield).

By analysis this product was found to contain C 57.6% wt; and H 5.0% wt.The compound 3,4,5-trihydroxyallylbenzoate (C₁₀ H₁₀ O₅) requires C 57.1%wt; and H 4.8% wt.

EXAMPLE 18

10 Parts of 3,4,5-trihydroxybenzoic acid (obtained from Aldrich ChemicalCompany) was added to a stirred mixture containing 35 parts ofhexa-2,4-dien-1-ol (also obtained from Aldrich Chemical Company) and 0.5parts of toluene-4-sulphonic acid. The mixture obtained was stirred atbetween 90° and 100° C. for 24 hours. A viscous dark brown liquid wasobtained which did not contain any 3,4,5-trihydroxybenzoic acid, asevaluated by comparative thin layer chromatography. This viscous liquidwas dissolved in 200 parts of acetone and 200 parts of isopropanol. 10Parts of this solution were evaporated to dryness, to give 1.0 part of alight brown solid.

By analysis this compound was found to contain C 74.7% wt; and H 8.5%wt.

EXAMPLE 19 Preparation of2,4-dithio-6(4-(hexa-2,4-dienoylamino)phenyl)amino-s-triazine

A solution containing 13.8 parts of 4-nitroaniline (obtained fromAldrich Chemical Company) dissolved in 160 parts of acetone and 20 partsof water was added dropwise, over 30 minutes, to a stirred suspension of18.6 parts of cyanuric chloride, 240 parts of acetone and 200 parts ofcrushed ice. The temperature was maintained at less than 5° C. byimmersing the reaction vessel in a bath containing crushed ice andwater. The pH of the mixture was maintained at between 6 and 7 by thedropwise addition of 53 parts of aqueous 2N sodium carbonate solution.After stirring for a further three hours at below 5° C., the reactionmixture was filtered, and the filter cake washed well with cold water(20° C.). The filter cake was stirred with 300 parts of water, and asuspension containing 328 parts of sodium hydrogen sulphide partiallydissolved in 600 parts of water was added. This mixture was heated atthe boil (about 100° C.) under reflux conditions for 16 hours. Aftercooling to 20° C., the reaction mixture was neutralised by the additionof 300 parts of glacial acetic acid. A grey solid was formed which wascollected by filtration and washed with cold water (20° C.). The solidwas then stirred with 600 parts of aqueous N sodium carbonate solution,heated to 60° C., and stirred for 30 minutes at 60° C. The solution soformed was filtered hot, cooled to 15° C. and 40 parts of glacial aceticacid were added slowly over one hour.

A solid (10.45 parts, 34.9% yield) was precipitated and this wasisolated by filtration, washed with water and dried at 60° C. for 24hours.

By analysis the product was found to contain C 36.1% H 3.2% wt; N 23.0%wt; and S 22.8% wt. 2,4-Dithio-6(4-aminophenyl)amino-s-triazine (C₉ H₉N₅ S₂) requires C 43.0% wt; H 3.6% wt; N 27.9% wt; and S 25.5% wt.

5 Parts of 2,4-dithio-6(4-aminophenyl)-amino-s-triazine, (prepared asdescribed previously) were stirred with 200 parts of dimethylformamideand 200 parts of acetone. The mixture was cooled to between 5° and 10°C. by immersion in a cooling bath containing ice and water. A solutionof 3.5 parts of hexa-2,4-dienoyl chloride (prepared as described in partA of Example 1) dissolved in 10 parts of acetone, was added dropwise tothe stirred reaction mixture over 30 minutes, maintaining the internaltemperature at between 5 and 10° C., and the pH of the mixture atbetween 5 and 6 by dropwise addition of 10 parts of aqueous 2N sodiumcarbonate solution. After stirring for one hour, 5 parts of aqueous 10Nsodium hydroxide were added, and the reaction mixture stirred for 16hours whilst allowing the temperature to rise to 20° C. 5 Parts ofglacial acetic acid were then added, and the mixture was poured into 700parts of water. The product (4.52 parts, 74.7% yield) was isolated byfiltration, washed with water, dried at 60° C. for 24 hours, stirredwith 200 parts of chloroform for four hours at 20° C., filtered, washedwith chloroform and dried at 60° C. for three hours.

By analysis the product was found to contain C 49.6% wt; H 4.8% wt; andN 19.5% wt. The compound2,4-dithio-6(4-(hexa-2,4dienoylamino)phenyl)-amino-s-triazine (C₁₅ H₁₅ON₅ S₅) requires C 52.2% wt; H 4.3% wt; and N 20.3% wt.

EXAMPLES 20 to 48

Samples of brass-coated steel wire, of the type used in reinforced carand truck tyres, were cut into 10 cm lengths and degreased by immersionin 1,1,2,2-tetrachloroethylene at 120°C. The degreased wire samples wereimmersed in 0.5% w/v solutions of products of Examples 1 to 19 or ofmixtures of products of Examples 1 to 19, the concentration of themixture being 0.5% w/v. The solvent employed depended on the product ormixture, and is indicated in Table One. After 30-40 seconds immersionthe samples were removed from the solutions and dried in a stream ofcold air. The treated samples, together with several untreated wiresamples, were subjected to a corrosion test as set out hereafter.

Before being subjected to this corrosion test, one end of each wiresample was immersed, to approx. 0.2 cm length, in butyl rubber paint for5-10 seconds. The paint was allowed to dry for an hour at 20° C. Thewire samples so treated were then subjected to a corrosion test byimmersing in distilled water at 20° C., ensuring that the rubber-treatedend of the cord was submerged, and the unpainted end of the cordprotruded above the surface of the water. After 20 hours, the cords wereremoved from the water and allowed to dry in air at 20° C. The degree ofcorrosion was then estimated visually. The criteria used to assign aparticular corrosion level to a treated cord are set out hereafter inNotes to Table One.

                  TABLE One                                                       ______________________________________                                        Example                                                                              Material                    Corrosion                                  or     deposited Solvents          level                                      Comp.  on cord   % volume          visual                                     Example                                                                              (a)       Ethanol  DMF   Toluene                                                                              rating (b)                             ______________________________________                                        20     1(B)      90       10    --     4                                      21     2(B)      80       20    --     3                                      22     3(B)      75       25    --     3                                      23     4         75       25    --     2                                      24     5(B)      84       16    --     6                                      25     6         84       16    --     8                                      26     7(B)      84       16    --     3                                      27     8         90       10    --     4                                      28     9(B)      84       16    --     1                                      29     10(B)     76       24    --     0                                      30     11        90       10    --     1                                      31     12        100      --    --     7                                      32     13        50       --    50     0                                      33     14        84       --    16     2                                      34     15        84       --    16     5                                      35     16(B)     100      --    --     7                                      36     17        100      --    --     3                                      37     18        100      --    --     2                                      38     19        70       30    --     6                                      39     1(B)50    85       15    --     3                                             2(B)45                                                                 40     1(B)45      86.5     13.5                                                                              --     5                                             2(B)45                                                                        17 10                                                                  41     1(B)40    88       12    --     1                                             2(B)40                                                                        17 20                                                                  42     1(B)33.3  90       10    --     2                                             2(B)33.3                                                                      17 33.3                                                                43     3(B)50    75       25    --     1                                             4 50                                                                   44     3(B)40    80       20    --     1                                             4 40                                                                          17 20                                                                  45     9(B)50    92        8    --     1                                             17 50                                                                  46     9(B)40    84       16    --     0                                             10(B)40                                                                       17 20                                                                  47     16(B)50   90       10    --     6                                             2(B)50                                                                 48     16(B)40   92        8    --     6                                             2(B)40                                                                        17 20                                                                  A      NONE      --       --    --     9                                      B      NONE      --       --    --     10                                     C      NONE      --       --    --     10                                     D      NONE      --       --    --     9                                      E      NONE      --       --    --     8                                      F      NONE      --       --    --     10                                     ______________________________________                                         Notes to Table One                                                            (a)The number, or number and letter, refers to the example, or portion of     the example, in which the preparation of the compound is described.      

In Examples 39 to 48 a mixture of additives was used, and the numberadjacent the reference to the additive refers to the percentage byweight of each additive in the mixture.

NONE indicates the wire had been degreased but not subjected to anyfurther treatment.

(b) The corrosion level visual rating is as follows:

    ______________________________________                                        Corrosion level                                                               visual rating                                                                           Description of cord after corrosion test                            ______________________________________                                         9-10     Very severe corrosion: very little evidence                                   of a golden lustrous layer on the cord surface,                               which is covered with black and red corrosion                                 products.                                                           7-8       Severe corrosion: some isolated areas are                                     still a lustrous golden colour. The corroded                                  areas of the cord are mainly red with some                                    black corrosion evident.                                            5-6       Some corrosion: approximately 50% of the                                      cord has maintained the original lustrous                                     sheen. In remaining areas red corrosion                                       products predominate.                                               3-4       Slight corrosion: most of the cord is                                         clean and lustrous. Occasional small areas                                    of red corrosion are evident.                                       1-2       Trace corrosion: only the slightest evidence                                  (a few red spots) are observed on the                                         lustrous golden cord.                                               0         No corrosion: the shiny golden surface is                                     unaffected, and is identical with untreated                                   cord.                                                               ______________________________________                                    

EXAMPLES 49 to 65

Samples of single strand brass-coated steel wire, of the type used inreinforced car and truck tires, were cut into 40 cm lengths anddegreased by immersion in 1,1,2,2-tetrachloroethylene at 120° C.

Products of some of Examples 1 to 19 were dissolved in 25 cm³ of asuitable solvent (N,N-dimethylformamide or toluene) and the solutionsdiluted to a total volume of 200 cm³ using industrial grade methylatedspirits to give 0.2% w/v solutions of the additive.

The degreased wire samples (12 for each experiment) were immersed in thesolutions prepared as described previously for 30 minutes at 50° C. Thesamples were then removed and rinsed with industrial grade methylatedspirits. The treated wire samples were dried in air at ambienttemperature and then stored in sealed glass tubes.

Ten wires were selected from each sample tube. The selected wires weremoulded into an uncured SBR tire compound and the rubber was cured at115° C. for 23 minutes, holding each wire in a straight position in themould under a load of one kg.

The samples obtained were held for 24 hours at ambient temperature andsplit into two groups of five samples. One set of five was stored at50±5% relative humidity and 23°±2° C. for 24 hours. The other set offive was placed in an autoclave having a steam saturated atmosphere at120°±2° C. for 24 hours.

The two sets of samples were then subjected to tensile testing using theprocedure described hereinafter.

Each sample was placed into a fixed slotted holder in such a manner thata wire was centrally orientated through the slot and was in the sameaxis as the pulling grip. The wire was then held by the pulling grip andpulled out of the moulded rubber block at a draw rate of 50 mm/minute.

The procedure was repeated for each wire moulded in the rubber. Thetensile test was carried out at a temperature of 23°±2° C. The testprocedure used corresponds generally with ASTM Test Method D 2229.

Further details of the material deposited on the wire and the results ofthe tensile tests are set out in Table Two.

                  TABLE Two                                                       ______________________________________                                        Example    Material                                                           or         deposited                                                          Comp.      on cord    Adhesion (N)                                            Example    (a)        Initial Steam Aged                                      ______________________________________                                        49         1(B)       220     57                                              50         2(B)       231     70                                              51         3(B)       220     47                                              52         4          210     54                                              53         5(B)       238     58                                              54         6          247     67                                              55         7(B)       205     62                                              56         8          224     72                                              57         9(B)       248     41                                              58         10(B)      247     88                                              59         11         163     78                                              60         12         205     24                                              61         14         175     33                                              62         16         238     70                                              63         17         216     62                                              64         18         210     53                                              65         19         143     39                                              G          NONE       219     58                                              ______________________________________                                    

I claim:
 1. A compound which contains a ligand group selected from atriazole, a thiazole, a benzotriazole, a naphthotriazole, a2-mercaptothiazole, or a 2-mercaptobenzothiazole and a group of theformula:

    --NH--TAZ(NR.sub.2).sub.2

    or

    --NH--TAZ(NHR.sub.2).sub.2

where R is a hydrocarbyl group which is either a saturated hydrocarbylgroup containing at least six but not more than 30 carbon atoms or anunsaturated hydrocarbyl group having a chain length of at least threebut not more than 30 carbon atom; and TAZ is a triazine ring.
 2. Acompound which contains a ligand group, selected from a benzothiazole, a2-mercaptobenzothiazole, and a group of the formula:

    --XR.sub.n

where X is a linking group, which contains at least one hereto-atom,selected from an amino, an amido, a carbonyloxy, a 1,4-phenylene, asubstituted or unsubstituted triazinyl, and combinations of thesegroups; R is a hydrocarbyl group which is either a saturated hydrocarbylgroup containing at least six but not more than 30 carbon atoms or anunsaturated hydrocarbyl group having a chain length of at least threebut not more than 30 carbon atom; and n is an integer which has a valueof at least one.
 3. A compound selected from the group consistingof:6(2,4-bis(allylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole;6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole;5(2,4-bis(diallylamino)-s-triazin-6-ylamino)-benzo-triazole;5(2,4-bis(n-octadecylamino)-s-triazin-6-ylamino)-benzo-triazole;5(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)-benzo-triazole; and6(2,4-bis(di-n-octylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole.4. A compound in accordance with claim 3 wherein said compound is6(2,4-bis(diallylamino)-s-triazin-6-ylamino)-2-mercaptobenzothiazole.